Polymer pendant ligand chemistry, 4. Recovery of precious metal ions from strongly acidic solution with a polymer-supported o-phenylenediamine hydrochloride ligand

We report on the synthesis and reactivity of a polymer-supported o-phenylenediamine hydrochloride ligand, PS-PDHC, using macroporous 6% crosslinked polystyrene-divinylbenzene beads. The PS-PDHC ligand was found to be highly selective to AuCl₄⁻ ions in strongly acidic solutions in the presence of other precious metal ions, PdCl₄²⁻, PtCl₄²⁻, RhCl₆³⁻, and RuCl₅²⁻ (selectivity values: 2.5, Au/Pd; 7.5, Au/Pt; 7, Au/Rh; 2.2, Au/Ru) as well as other transition metal ions, Fe ³⁺, Cr³⁺, CU²⁺, Nit+, and Mn²⁺. The sorption capacity, selectivity, kinetics of removal and recovery, and solution isotherms have been determined for AuCl₄⁻ ions in competition with the above-mentioned metal ions. The relative ease of formation of the anionic complex in 0.5 M HCI, AuCl₄⁻ was thought to be the primary reason for its selective ability to bind to the PS-PDHC ligand by an anion-exchange mechanism. Therefore, the effect of the HCI concentration on the kinetics of AuCl₄⁻ ion removal from solution was also investigated to clearly show that raising the pH from 0 to 5 caused a dramatic decrease in rate. The AuCl₄⁻ ion can be recovered quantitatively from the PS-PDHC beads using a 5% thiourea solution in 0.1 M HCl, allowing the polymer-supported ligand to be reused.     

麻黄碱旋光异构化新工艺研究

介绍了将盐酸L-麻黄碱直接经过乙酰异构化、酸化水解工艺过程异构化为盐酸D-伪麻黄碱的新工艺,其工艺的优化条件是盐酸L-麻黄碱与乙酸酐的配比(摩尔比)为1∶3.5,酰化异构化温度100℃,酰化异构化时间7 h。酸化水解步骤所加入的浓盐酸(36.5%)与原料的配比(摩尔比)1.5∶1,酸化水解温度90℃,酸化水解时间8 h,产品盐酸D-伪麻黄碱收率大于98%。     

盐酸吗啉脒胍的合成研究

以吗啉和盐酸为原料合成盐酸吗啉,使其与双氰胺反应制备盐酸吗啉脒胍。重点讨论了原料配比、加料顺序、反应时间及溶剂等因素对合成工艺的影响。研究表明：吗啉：浓盐酸=1．06∶1(摩尔比),合成盐酸吗啉的收率可达98．27％,且加料顺序对反应无明显影响；以二甲苯为溶剂,盐酸吗啉：双氰胺=0．8∶1(质量比),反应时间为3．5h,盐酸吗啉脒胍的收率为97．01％。两步反应总收率可达96．97％。     

盐酸曲美他嗪的合成

研究一种冠状动脉血管扩张剂盐酸曲美他嗪的合成方法。以六水哌嗪为起始原料,经酰化、Mannich反应、水解、成盐反应制得目标化合物。目标化合物的结构经熔点测定、红外及1 H-NMR谱确证,总收率为29.2%,经HPLC检测纯度为98.5%。该合成方法成本较低、操作简便、条件温和,适于工业生产。     

顶空气相色谱法测定盐酸托泊替康中残留有机溶剂

采用顶空气相色谱法测定盐酸托泊替康中的残留有机溶剂。载气为氮气,检测器为FID,色谱柱为DB-624毛细管柱,柱温为55℃,检测器温度为250℃,进样口温度为250℃,测定盐酸托泊替康中甲醇、丙酮、乙腈、乙酸乙酯和二氧六环的残留量。结果显示5种溶剂达到完全分离,在考察的质量浓度范围内具有良好的线性关系,r均达到0.999,平均回收率为98.6%～99.9%。用所建立的分析方法测定盐酸托泊替康中的残留有机溶剂,结果准确、可靠。     

电合成芳醛生产中的监控分析方法

本工作研究了盐酸羟胺法测定芳醛的适宜条件，测定了本方法的精密度和准确度，结果令人满意。用此方法对电合成芳醛生产中料液及产品中的醛含量进行了分析，测定结果和色谱法、电位滴定法测定一致。     

L-高丝氨酸内酯盐酸盐的合成研究

从L-蛋氨酸出发,分别采用"一锅法"和两步法探讨了L-高丝氨酸内酯盐酸盐的合成。这两种方法对常用的三步法进行了改进,简化了合成过程,减少了碘甲烷的用量,缩短了反应时间,提高了收率。两步法虽增加了一次分离过程,但却大大简化了最终产品的纯化过程,有效避免了产品中无机盐的引入,总收率可达到73.4%。     

Sinomenine Hydrochloride Promotes TSHR-Dependent Redifferentiation in Papillary Thyroid Cancer

Radioactive iodine (RAI) plays an important role in the diagnosis and treatment of papillary thyroid cancer (PTC). The curative effects of RAI therapy are not only related to radiosensitivity but also closely related to the accumulation of radionuclides in the lesion in PTC. Sinomenine hydrochloride (SH) can suppress tumor growth and increase radiosensitivity in several tumor cells, including PTC. The aim of this research was to investigate the therapeutic potential of SH on PTC cell redifferentiation. In this study, we treated BCPAP and TPC-1 cells with SH and tested the expression of thyroid differentiation-related genes. RAI uptake caused by SH-pretreatment was also evaluated. The results indicate that 4 mM SH significantly inhibited proliferation and increased the expression of the thyroid iodine-handling gene compared with the control group (p < 0.005), including the sodium/iodide symporter (NIS). Furthermore, SH also upregulated the membrane localization of NIS and RAI uptake. We further verified that upregulation of NIS was associated with the activation of the thyroid-stimulating hormone receptor (TSHR)/cyclic adenosine monophosphate (cAMP) signaling pathway. In conclusion, SH can inhibit proliferation, induce apoptosis, promote redifferentiation, and then increase the efficacy of RAI therapy in PTC cells. Thus, our results suggest that SH could be useful as an adjuvant therapy in combination with RAI therapy in PTC.     

非水滴定法测定盐酸水苏碱的含量

建立了测定盐酸水苏碱含量的非水滴定法。以冰醋酸作溶媒,以0.2%结晶紫为指示剂,用0.1 mol/L标准高氯酸溶液进行滴定。平均回收率为98.74%,RSD为0.68%(n=6)。本方法简单、可靠、准确。